Synthesis, characterization, and stability of Fe-MCM-41 for production of carbon nanotubes by acetylene pyrolysis

Fe-substituted MCM-41 molecular sieves with ca. 1, 2, and 3 wt % Fe were synthesized hydrothermally using different sources of colloidal silica (HiSil and Cab-O-Sil) and characterized by ICP, XRD, N2 physisorption, UV-vis, EPR, TPR, and X-ray absorption. Catalysts synthesized from Cab-O-Sil showed higher structural order and stability than those from HiSil. The local environment of Fe in the mesoporous material as studied by UV-vis reveals the dominance of framework Fe in all the as-synthesized Fe-MCM-41 samples. Dislodgement of some Fe species to extraframework location occurs upon calcination, and this effect is more severe for Fe-MCM-41 (2 wt %) and Fe-MCM-41 (3 wt %), as confirmed by EPR and X-ray absorption. These materials have been used as catalytic templates for the production of carbon nanotubes (CNTs) by acetylene pyrolysis at atmospheric pressure. A relationship between the Fe loading in MCM-41 and the carbon species produced during this reaction has been established. Using our optimized conditions for this system, Fe-MCM-41 with ca. 2 wt % Fe showed the best results with particularly high selectivity for single-wall carbon nanotube (SWNT) production. This catalyst was selective for carbon nanotubes with a low amount of amorphous carbon for a narrow range of temperatures from 1073 to 1123 K. To account for the different selectivity of these catalysts for CNTs production, the local environment and chemical state of Fe in the used catalyst was further probed by X-band EPR.     

Absence of renormalization group pathologies near the critical temperature. Two examples

We consider real-space renormalization group transformations for Ising-type systems which are formally defined by $$\exp \left[ { - H'(\sigma ')} \right] = \sum\limits_\sigma {T(\sigma ,\sigma ')} \exp \left[ { - H(\sigma )} \right]$$ whereT(σ, σ′) is a probability kernel, i.e., ∑_σ′ T(σ,σ′) = 1 for every configuration σ. For each choice of the block spin configuration σ′, let σ′, let μ_σ′ be the measure on spin configurations σ which is formally given by taking the probability of σ to be proportional toT(σ, σ′) exp[?H(σ)]. We give a condition which is sufficient to imply that the renormalized HamiltonianH′ is defined. Roughly speaking, the condition is that the collection of measures μ_σ′ is in the high-temperature phase uniformly in the block spin configuration σ′. The proof of this result uses methods of Olivieri and Picco. We use our theorem to prove that the first iteration of the renormalization group transformation is defined in the following two examples: decimation with spacingb = 2 on the square lattice with β < 1.36β _c and the Kadanoff transformation with parameterp on the trian gular lattice in a subset of the β,p plane that includes values of β greater than β _c .     

Near infrared electronic spectrum of TCNQ mono-valent anion

The high resolution near infrared electronic spectrum of TCNQ anion dissolved in 2-methyltetrahydrofuran glass at 77 K has been determined. The absorption bands are interpreted as simple progressions of two molecular vibrations in a single electronic excited state with ν₀₀ = 11661 cm^?1. The molecular vibrations (ω′₁ = 1264 ± 3 cm^?1, ω′₂ = 335 ± 3 cm^?1) of the vibrational progression agree well with observed Raman active transitions. The experimental data do not require the presence of two electronic transitions in the 1.3 to 2.1 eV region, contrary to what had been assumed previously on the basis of less well resolved room temperature spectra.